Polyglycidyl ethers

ABSTRACT

The present invention describes the production of high molecular weight polyglycidyl ethers.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a division of Ser. No. 081,950, filed Oct. 4, 1979;now, U.S. Pat. No. 4,339,389, issued July 13, 1982.

Related subject matter is disclosed in applicant's prior application,Ser. No. 026,858 filed Apr. 4, 1979; now U.S. Pat. No. 4,216,343 issuedAug. 5, 1980.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to products and processes useful in themanufacture of synthetic resins from polyglycidyl materials.

2. Description of the Art Practice

The products of the present invention are obtained from raw materialssubjected to hydroformylation. Hydroformylation is basically defined asthe addition of a formyl group through the reaction of an unsaturatedcompound with carbon monoxide and hydrogen. The basic technology for themanufacture of hydroformylated products and consequently theirderivatives is amply set out hereinafter.

In the past several attempts have been made to prepare hydroformylatedproducts or similar materials such as is described in U.S. Pat. No.2,437,600 to Gresham et al issued Mar. 9, 1948. The Gresham patentrelates to the synthesis of organic oxygen containing compounds, inparticular aldehydes. U.S. Pat. No. 2,533,276 to McKeever et al issuedDec. 12, 1950 describes ester-acetals obtained with cobalt catalysts.U.S. Pat. No. 2,599,468 to McKeever issued June 3, 1952 describes theprocess of preparing nonadecyl glycols.

U.S. Pat. No. 3,040,090 issued June 19, 1962 to Alderson et al discussesthe reaction of hydrocarbons with aldehydes and higher alcohols inmethanol to prepare organic oxy compounds. The Alderson et al patentsets forth a number of metallic catalysts which may be employed ineffecting the reactions described therein.

In U.S. Pat. No. 3,043,871 issued July 10, 1962 to Buchner et al theproduction of heptadecane-dicarboxylic acid is described. Foreman et alin U.S. Pat. No. 3,227,640 issued Jan. 4, 1966 describes the productionof olefinically unsaturated alcohols which are of use in manufacturingsome of the end products of the present invention. Bernardy et aldescribe oxyalkylated dimethylol and trimethylol alkanes in U.S. Pat.No. 3,290,387 issued Dec. 6, 1966. U.S. Pat. No. 3,420,898 issued to VanWinkle et al on Jan. 7, 1969 discusses the use of cobalt complexes withcertain phosphine compounds in the production of primary alcohols withcarbon monoxide and hydrogen.

U.S. Pat. No. 3,530,190 issued Sept. 22, 1970 to Olivier discusseshydrocarbonylation of olefins using certain metal salts. The foregoingreference also discusses the recovery of the complexed metal catalyst.In a patent to Ramsden issued Jan. 16, 1973 as U.S. Pat. No. 3,711,560,the production of polyolefins and other oxygenated organic compoundswhich are polyunsaturated is discussed.

In U.S. Pat. No. 3,787,459 issued Jan. 22, 1974 to Frankel a process isdescribed for converting unsaturated vegetable oil into formyl productswhich are subsequently reduced to the corresponding hydroxymethylderivative to oxidized to the corresponding carboxy products. U.S. Pat.No. 3,899,442 issued Aug. 12, 1975 to Friedrich discusses acomplementary system to that of the Frankel patent whereby rhodiumcatalysts are recovered from the spent hydroformylation reactants.Frankel, again in U.S. Pat. No. 3,928,231, issued Dec. 23, 1975discusses a process of preparing carboxy acid products in high yieldswhile minimizing isomerization of the starting unsaturated vegetableoil. Miller et al in U.S. Pat. No. 4,093,637 issued June 6, 1978discusses the use of formyl stearic acid to prepare bisacyloxymethylstearic acid which is stated to be useful as a plasticizer.

U.S. Pat. No. 3,931,332 issued Jan. 6, 1976 to Wilkes discusseshydroformylation reactions in which the destructive disassociation ofthe catalyst is inhibited by the presence of organic nitrogen compounds.Reichspatentamt Patentschrift No. 745,265 to Mannes et al published Mar.1, 1944 discusses the preparation of dicarboxylic acids and their salts.In Bundesrepublik Deutschland Pat. No. 965 697 issued June 13, 1957 toBlaser and Stein the reaction of unsaturated alcohols and theirderivatives with metal carbonyls and carbon monoxide is discussed. Aby-product which is obtained through the technology of Blaser et alincludes substantial amounts of monoformylated product. Similarly aformylation technique which results in a monoformylated product whenusing unsaturated alcohols is discussed in an article by Ucciani et alin the Bull. Soc. Chim. (France) 1969 p. 2826-2830. SimilarlyBundesrepublik Pat. No. 1,054,444 published Apr. 9, 1959 to Waldmann andStein discusses the treatment of unsaturated fatty substances withformaldehyde in the presence of a carboxylic anhydride and an acidiccatalyst to provide formyl products.

Substantial work has been done on the production of varioushydroformylated products by the United States Department of Agricultureat its Regional Research Laboratories. For example, in an article by Roeentitled "Branched Carboxylic Acids from Long-Chain UnsaturatedCompounds and Carbon Monoxide at Atmospheric Pressure" published at J.Am. Oil Chemists' Soc. 37, p. 661-668 (1960). The production by directcarboxylation at atmospheric pressure of unsaturated acids with carbonmonoxide or formic acid is discussed. Polyols from hydroformylation aredescribed in an article entitled "Preparation of2-Decyl-2-Hydroxymethyl-1,3-Propanediol from Dodecanol and PetroselinicAcid" by Holmes et al at J. Am. Oil Chemists' Soc. 42, No. 10, pages833-835 (1965). The hydroformylation of unsaturated fatty esters isdiscussed by Frankel et al at J. Am. Oil Chemists' Soc. 46, p. 133-138(1968). Frankel has also reported a selective catalyst system for thehydroformylation of methyl oleate utilizing rhodium catalyst in thepresence of triphenylphosphine in an article entitled "Methyl9(10)-Formylstearate by Selective Hydroformylation of Oleic Oils" at J.Am. Oil Chemists' Soc. 48, p. 248-253 (1971).

In a paper presented at the American Oil Chemists' Society meeting inAtlantic City, N.J. in 1971, Dufek et al discusses the esterificationand transesterification of dicarboxylic acids under the title"Esterification and Transesterification of 9(10)-Carboxystearic Acid andIts Methyl Esters". The foregoing article was published at J. Am. OilChemists' Soc. 49 (5) p. 302-306 (1972). Frankel, again, discusses theuse of specific catalysts to obtain hydroformylated products in anarticle titled "Selective Hydroformylation of Polyunsaturated Fats Witha Rhodium-Triphenylphosphine Catalyst", J. Am. Oil Chemists' Soc. 49, p.10-14 (1972). Friedrich at Vol. 17, No. 3 of Ind. Eng. Chem. Prod. Res.Dev. (1978) presents an article entitled "Low-Pressure Hydroformylationof Methyl-Oleate With an Activated Rhodium Catalyst".

Pryde, working with Frankel and Cowan discuss hydroformylation via theoxo reaction, Koch carboxylation and Reppe carbonylation in an articleentitled "Reactions of Carbon Monoxide with Unsaturated Fatty Acids andDerivatives: A Review", reported at J. Am. Oil Chemists' Soc. 49, p.451-456 (1972).

Friedrich discusses the hydroformylation of unsaturated esters combinedwith catalyst recovery in an article entitled "Hydroformylation ofMethyl Oleate with a Recycled Rhodium Catalyst and Estimated Costs for aBatch Process" at J. Am. Oil Chemists' Soc. 50, p. 455-458 (1973). Asimilar area of technology is also reported by Frankel et al in anarticle entitled "Hydroformylation of Methyl Linoleate and Linolenatewith Rhodium-Triphenylphosphine Catalyst" from I&EC Product Research &Development, Vol. 12, p. 47-53 (1973).

Certain condensation polymers prepared from pentaerythritol acetalderivatives are reported in an article "Poly(Amide-Acetals) andPoly(Ester-Acetals) from Polyol Acetals of Methyl (9(10)-Formylstearate:Preparation and Physical Characterization" reported at J. Am. OilChemists' Soc. 53, p. 20-26 (1976). Compounds obtained throughhydroformylation technology useful as plasticizers are discussed in aFrankel et al article entitled "Acyl Esters from Oxo-DerivedHydroxymethylstearates as Plasticizers for Polyvinyl Chloride" printedin the J. Am. Oil Chemists' Soc. 52, p. 498-504 (1975).

Friedrich in an article entitled "Oxidation of Methyl Formylstearatewith Molecular Oxygen" at J. Am. Oil Chemists' Soc. 53, p. 125-129(1976) reports the use of air or oxygen to form methyl carboxystearatefrom methyl formylstearate in an emulsion with a soluble rhodiumcomplex. The reuse of catalyst in hydroformylation reactions isdescribed by Awl in an article entitled "Hydroformylation with RecycledRhodium Catalyst and One-Step Esterification-Acetalation: A Process forMethyl 9(10)-Methoxymethylenestearate from Oleic Acid" which is printedin J. Am. Oil Chemists' Soc. 53, p. 190-195 (1976).

Useful diols for resin purposes are described in U.S. Pat. No. 2,933,477issued Apr. 19, 1960 to Hostettler. Nonadecanediols are described asbeing utilized in urethane formulations in U.S. Pat. No. 3,243,414 toDeWitt et al issued Mar. 29, 1966. The production of triols which arenot particularily useful in resins due to the close positioning of thehydroxyl groups is reported in Improved Synthesis of1,1,1-trimethylolalkanes from Hexanal and Nonanal J. Am. Oil Chemists'Soc. 45, p. 517 (July 1968) by Moore and Pryde. Polyols similar to thosedescribed by Moore et al are disclosed in British Pat. No. 867,230published May 3, 1961.

Frankel et al in a paper entitled Catalytic Hydroformylation andHydrocarboxylation of Unsaturated Fatty Compounds at J. Am. OilChemists' Soc. 54, p. 873A (1977) also describes formylation technology.Frankel also describes the use of carbonyl metallic compounds inhydroformylations in an article entitled "Catalytic Hydroformylation ofUnSaturated Fatty Derivatives with Cobalt Carbonyl" at J. Am. OilChemists' Soc. 53, p. 138-141 (1976). The use of esters of variouscarboxystearic acids is discussed by Dufek et al in an article entitled"Some Esters of Mono-, Di-, and Tricarboxystearic Acid as Plasticizers:Preparation and Evaluation" at J. Am. Oil Chemists' Soc. 53, p. 198-203(1976). Dufek et al also report catalyst recovery in an article entitled"Recovery of Solubilized Rhodium from Hydroformylated Vegetable Oils andTheir Methyl Esters" in J. Am. Oil Chemists' Soc. 54, p. 276-278.

Frankel discusses hydroformylation generally in an article entitledSelective Hydroformylation of Unsaturated Fatty Acid Esters at AnnalsN.Y. Academy of Sciences 214:79 (1973). Catalyst technology is reviewedat Recent Developments in Hydroformylation Catalysis in Catal. Rev. 6(1) page 49 et seq. (1972).

Dufek alone at J. Am. Oil Chemists' Soc. 55, p. 337-339 (1978) reportson the conversion of methyl 9(10) formylstearate in an article entitled"Conversion of Methyl 9(10)-Formylstearate to Carboxymethylstearate".

Acetal esters obtainable through hydroformylation technology arereported by Adlof et al in an article entitled "Preparation andSelective Hydrolysis of Acetal Esters" at J. Am. Oil Chemists' Soc. 54,p. 414-416 (1977). Selective catalyst systems are again reported byFrankel in the J. Am. Oil Chemists' Soc. 54, p. 873a-881a (1977) in anarticle entitled "Catalytic Hydroformylation and Hydrocarboxylation ofUnsaturated Fatty Compounds".

The plasticization of polyvinylchloride resins is also reported inpatent applications coded P.C. 6333 and 6375 bearing respectively thetitles "Acetoxymethyl Derivatives of Polyunsaturated Fatty Triglyceridesas Primary Plasticizers for Polyvinylchloride", and "Alkyl9,9(10,10)-Bis(acyloxymethyl) octadecanoates as Primary Plasticizers forPolyvinylchloride". P.C. 6333 issued as U.S. Pat. No. 4,083,816 on Apr.11, 1978. P.C. 6375 issued as U.S. Pat. No. 4,093,637 on June 6, 1978.

Each of the foregoing to the extent that it is applicable to the presentinvention is herein incorporated by reference.

The basic purpose of the present invention is to describe as endproducts the polyglycidyl ethers of high molecular weight polyhydricalcohols. These polyglycidyl ethers are highly useful as curing agentsfor amines and amides in the coating arts. Of course several other usesof the technology embodied in this patent are readily apparent.

Throughout the specification and claims of the present inventionpercentages and ratios are by weight and temperatures are in degrees ofCelsius unless otherwise indicated. The terms polyglycidyl ether andoxirane or epoxy of the high molecular weight polyhydric alcohols areused synonymously.

SUMMARY OF THE INVENTION

The present invention is a composition of matter comprising apolyglycidyl ether of a polyol selected from the group consisting of:

    H(CH.sub.2).sub.h CH(CH.sub.2 OH)(CH.sub.2).sub.k CH.sub.2 OH (a)

and

    CH.sub.3 (CH.sub.2).sub.m [C(CH.sub.2 OH).sub.2 ].sub.n (CH.sub.2).sub.p [C(CH.sub.2 OH).sub.2 ].sub.q (CH.sub.2).sub.r [C(CH.sub.2 OH).sub.2 ].sub.s (CH.sub.2).sub.t CH.sub.2 OH                      (b)

and mixtures thereof wherein n plus s are integers the sum of which isfrom 1 to 3; k and t are 3 or greater; n, q, and s are 0 or 1; m throught are integers the sum of which is from 12 to 20; and, h plus k arenon-zero integers the sum of which is from 12 to 20.

DETAILED DESCRIPTION OF THE INVENTION

The polyglycidyl ethers of the present invention are obtained fromalcohols which are obtained in turn by hydroformylation processes.Hydroformylation is the process for the production of aldehydes fromolefinically unsaturated compounds by reaction with carbon monoxide andhydrogen in the presence of a catalyst. The aldehydes produced generallycorrespond to the compounds obtained by the addition of a hydrogen and aformyl group to an olefinically unsaturated group in the startingmaterial thus saturating the olefinic bond.

The useful products of the present invention are prepared byhydroformylating an unsaturated alcohol of the formula

    H(CH.sub.2).sub.a (CH═CH).sub.b (CH.sub.2).sub.c (CH═CH).sub.d (CH.sub.2).sub.e (CH═CH).sub.f (CH.sub.2).sub.g CH.sub.2 OH

where hereinafter (1) a and g are not equal to 0; (2) the integers bplus d plus f are equal to y which has a value of from 1 to 3; (3) thesum of the integers a plus c plus e plus g is equal to x; and (4) x plus2y is equal to from 13 to 21.

In the polyglycidyl ether (5) m through t are integers the sum of whichis from 12 through 20; (6) n plus q plus s are 1 through 3, and; (7) n,q, and s are 0 or 1, preferably such that the sum of m through t is from14 to 18 and x plus 2y is 15 to 19; and (8) k and t are each 3 orgreater. It is particularly preferred that h plus k are non-zerointegers the sum of which is from 12 to 20, preferably 14 to 18 andwhere h, m, k and t each are 4, 5 or 6 or greater. It is also preferredthat n and s are 0 and q is 1. Most preferably the starting raw materialis oleyl alcohol although linoleyl or linolenyl alcohol may be employed.It is, of course, noted that any number of synthetic unsaturatedalcohols may also be employed in the present invention. However, formost purposes the naturally occurring alcohols derived from plantsources are presently most convenient and inexpensive.

The unsaturated alcohol is reacted with hydrogen gas and carbon monoxidein the presence of a rhodium catalyst as later described to form thecorresponding formyl alcohol having the formula

    CH.sub.3 (CH.sub.2).sub.m [CH(CHO)].sub.n (CH.sub.2).sub.p [CH(CHO)].sub.q (CH.sub.2).sub.r [CH(CHO)].sub.s (CH.sub.2).sub.t CH.sub.2 OH

wherein the various subscript numbers are as previously described.

The addition of hydrogen and carbon monoxide is accomplished in practiceby conveniently adding stoichiometric amounts of the hydrogen and carbonmonoxide to give the formyl alcohol. To assure completeness of thereaction the amounts of hydrogen and carbon monoxide may be eachmaintained at from about 1.5:0.5 to about 0.5:1.5 molar ratio to oneanother. It is noted that the ratio is not critical as long as thepressure is maintained in the reaction vessel by the component gases andthat the amount of hydrogen is not so great as to substantially reducethe unsaturated starting material.

The rhodium catalyst as later described is necessary in thehydroformylation reaction in that it has been found that the use of themore conventional cobalt catalyst results in a substantial amount ofcross-linking gelation. It is believed that the gelation is due to thecoproduction of polyhemiacetals and polyacetals in competition with theproduction of the hydroformylated alcohol. It was at first believed bythe author that it would be necessary, even with a rhodium catalyst, toemploy the ester of the unsaturated alcohol e.g. oleyl acetate to avoidthe unwanted by-products. Of course, the ester is more expensive andeventually is converted to the alcohol in any event.

Higher yields of product are obtained through the use of the rhodiumcatalysts than if a cobalt catalyst is employed. It has also beenobserved that a much higher degree of isomerization of the double bondoccurs with a cobalt catalyst than with a rhodium catalyst.

The conditions for pressure and temperature during the hydroformylationare conveniently conducted at from about 90 degrees C. to about 170degrees C., preferably from about 110 degrees C. to about 130 degrees C.Above the higher temperatures listed above increased amounts of unwantedby-products are formed in the reaction mixture. The pressure conditionsare such that the pressure in the sealed system is maintained at fromabout 20 to about 500 atmospheres, preferably from about 30 to about 100atmospheres absolute during the hydroformylation.

The preferred end product obtained from conducting the foregoing processis 9(10) formyl octadecanol when the starting material is oleyl alcohol.The positioning of the 9(10) indicates that the product obtained is amixture of the 9 and 10 isomer with respect to the formyl group. Oneadditional reason for using a rhodium catalyst is that if a cobaltcatalyst were employed a considerable amount of terminal aldehyde wouldbe formed due to bond migration prior to the addition of the formylgroup. When the terminal aldehyde group is formed the resultant alcoholobtained by carrying out the remainder of the process is unsuitable formany of the purposes that the desired alcohols may be utilized. That is,it has been found that terminal aldehydes are high melting thusresulting in solid polyglycidyl ethers which require solvents and/orhigh temperatures for use as curing agents.

It should also be appreciated that if 9,12-linoleyl alcohol is thestarting material then the formyl alcohol so formed will be a 9(10),12(13) diformyloctadecanol. That is, the end product obtained here willactually be a mixture of the 9-12,9-13,10-12,10-13 diformyl alcohol.Similarly, without discussing all the particular isomers present when9,12,15-linolenyl alcohol is employed the product so obtained will be amixture of the 9(10),12(13),15(16) triformyloctadecanol isomers.

It is particularly important that the expensive rhodium catalyst isrecovered. This may be conveniently done by distillation of the formylalcohol leaving the rhodium in the residue. What is particularlysurprising is that the rhodium can be recovered from the distillate inthat the art would predict that when hydroformylating an unsaturatedalcohol that the products obtained would include considerable quantitiesof polyhemiacetals and polyacetals as a portion or all of the reactionproduct and that these products would not be recoverable bydistillation. Thus, not only is the desired end product achieved in ahigh degree of purity and yield through the use of the rhodium catalystbut the rhodium catalyst is recoverable in extremely high quantitiesfrom the reaction mixture.

It should also be emphasized that if the polyhemiacetals and polyketalswere formed in the reaction mixture that it is very likely that thereaction components would undergo a great change in viscosity to thepoint of forming a semi-solid product due to the extensive cross-linkingof the acetal and ketal linkages. Thus a substantial reason exists foravoiding the polyhemiacetal and polyacetal formation through the use ofa rhodium catalyst.

It may be stated that the polyacetal and polyhemiacetal formation mightbe prevented by the utilization of the corresponding unsaturated acid orits ester in place of the unsaturated alcohol. However, thissubstitution which eventually involves the acid ester is undesirable inthat an aqueous neutralization step is required which forms a soap as aby-product. The soap so formed then emulsifies the reaction products andthe water present to make separation extremely difficult thusdiminishing recovery of both the alcohol and the expensive catalyst.Thus the present invention is highly selective to both the unsaturatedalcohol and the particular rhodium catalyst so employed.

Any convenient source of rhodium may be employed as in the presentreaction mixture the rhodium catalyst is actually converted through thepresence of the hydrogen and carbon monoxide into its active form whichis a rhodium carbonyl hydride. Conveniently, the source of rhodium foruse in the rhodium catalyst may be rhodium metal, rhodium oxide, andvarious other rhodium salts such as rhodium chloride, rhodium dicarbonylchloride dimer, rhodium nitrate, rhodium trichloride and other similarmaterials.

The rhodium catalyst in the present hydroformylation reaction ispreferably present with a ligand such as a trisubstituted phosphine ortrisubstituted phosphite. The term trisubstituted includes both alkyland aryl compounds and the substituted compounds of the alkyl and arylcompounds. A particularly valuable ligand for the rhodium carbonylhydride is a triphenylphosphite or triphenylphosphine in that bothcompounds are particularly useful in minimizing migration of the doublebond thereby avoiding a large number of isomers with respect to theformyl group including the undesired terminal formyl compound aspreviously discussed. In general triaryl phosphines or triarylphosphitesmay be used for this purpose in the formation of the rhodium carbonylhydride ligand. In addition, the foregoing materials are extremelyvaluable in minimizing the undesired reaction of saturation of thedouble bond or the reduction formyl group. This frequently occurs in theabsence of such ligands because the rhodium catalyst functionsexcellently as a hydrogenation catalyst. That is the ligand tends toeliminate such side reactions.

In general anyone of several other additional ligands may be used withthe rhodium catalyst. Such additional ligands are discussed in theSelective Hydroformylation of Unsaturated Fatty Acid Esters by Frankelin the Annals N.Y. Academy of Sciences 214:79 (1973).

The various ligands are conveniently employed in mole ratio to therhodium metal content of the catalyst of from about 2 to 50 preferablyfrom 3 to 20. The rhodium catalyst based upon its metal content isconveniently employed in catalytic amounts preferably from about 20 ppmto about 10,000 ppm, most preferably from about 50 ppm to about 500 ppmby weight of the unsaturated alcohol.

The various formyl alcohols are useful as previously stated in preparingthe highly desired gem-bis(hydroxymethyl) alcohols. The alcohols may beformed from the foregoing formyl alcohols via a Tollens' reaction (aldolcondensation followed by a crossed-Cannizzaro reaction).

Schematically the Tollens' reaction is as described below: ##STR1##wherein the above formula R indicates an organic moiety, compound (I) isa hydroxymethyl aldehyde and MOH is a strong base.

The Tollens' reaction is thus carried out by reacting one mole of amonoformylated alcohol with two moles of formaldehyde in an inertatmosphere such as nitrogen. Where the formyl alcohol contains more thanone formyl group, two moles of formaldehyde are required for each formylgroup present. Thus, if the reactant is formyloctadecanol then two molesof formaldehyde are required for conversion to thegem-bis(hydroxymethyl) alcohol whereas if linoleyl alcohol is utilizedin the first instance to give a diformyloctadecanol then four moles offormaldehyde are required to obtain the di-geminaloctadecanol.Conveniently an excess of up to 1.5, preferably up to 1.2 times theamount of formaldehyde actually required to form the correspondinggem-bis-(hydroxymethyl) alcohol is employed in the present invention. Aconvenient manner of adding the formaldehyde in the Tollens' reaction isby using a methanol solution of formaldehyde.

The Tollens' reaction utilizes a strong base as both a reactant and acatalyst. Such strong bases include sodium, potassium or calciumhydroxide. Other strong bases such as carbonates or other hydroxides maybe used as well. The strong base is conveniently employed on anequivalent basis per formyl group to convert the formyl group to thehydroxy methyl group. The amount of base required in the Tollens'reaction is at least an equivalent of that required preferably up to1.5, most preferably up to 1.2 equivalents. The Tollens' reaction isconducted at a temperature of from about 0 degrees C. to about 100degrees C., preferably from about 20 degrees C. to about 70 degrees C.

The crude gem-bis(hydroxymethyl) alcohol so formed is washed with waterto remove any excess caustic and salts formed and then obtained in arelatively pure state by vacuum drying.

In obtaining the gem-bis(hydroxymethyl) alcohol of the present inventionthe crossed-Cannizzaro reaction predominates over the rate of reactionfor the simple Cannizzaro reaction.

The Cannizzaro reaction which is promoted by base, water, and heat isthe process by which an aldehyde reacts with itself to form thecorresponding alcohol and formate salt. That is, in the presentinvention the formyl group on the formyl alcohol reacts faster withformaldehyde to give the alcohol than does the formaldehyde react withitself despite the steric hinderance of the larger formyl alcoholmolecule.

It is also surprising that the formation of hemiacetal which may be acidor base catalyzed does not occur upon the addition of base to the formylalcohol while forming the intermediate hydroxymethyl formyl alcohol.Thus two potential side reactions, the Cannizzaro and the hemiacetalformation (and thereafter the acetal) which might be expected given thereactants and the processing condition involved do not in fact occur andthe useful alcohol is obtained in substantial quantities.

An alternative method of accomplishing the formation of the geminalalcohol is to use only about one-half the equivalent amount of theformaldehyde required in the Tollens' reaction thereby forming thecorresponding hydroxymethyl formyl alcohol via the aldol condensation.That is, the hydroxymethyl group is attached to the carbon in the alphaposition to the formyl group. Where a polyformyl alcohol is theintermediate product the formaldehyde is halved from that utilized inthe Tollens' reaction to give the corresponding polyhydroxymethylpolyformyl alcohol.

This variation of forming the geminal alcohol eliminates the need forthe strong base required in the Tollens' reaction and utilizes insteadonly catalytic amounts of base which may be either a weak or strongbase. A preferred weak base is triethylamine. Even here some care mustbe taken as it is possible even when using a weak base to obtaincompound (I) as the Cannizzaro reaction may compete with the aldolcondensation.

The hydroxymethyl formyl alcohol so formed by this alternative route isthen reduced to the alcohol conveniently by using hydrogen gas and asuitable hydrogenation catalyst such as copper chromite, or nickel, viaconventional hydrogenation practice or by lithium aluminum hydrideproduction. A significant advantage to the alternative route is theabsence of large amounts of salt and solvents needed in the Tollens'reaction route.

A distinct advantage in the geminal alcohol of the present invention isthat it is a liquid at room temperature and further has no tertiaryhydrogens which are a weak point for chemical attack on the molecule.

A mixture of the diol and the geminal alcohol is obtained by reactingthe unsaturated alcohol to obtain the corresponding formyl alcohol.Thereafter the formyl alcohol is split into two streams, the first ofwhich is processed as previously discussed to give the geminal alcoholwhile the second stream is reduced by hydrogenation to give the diol.The hydrogenation is generally carried out as discussed in thealternative route for preparing the geminal alcohol. The diol and thegeminal alcohol are then recombined in the desired proportions which arepreferably in a weight ratio of from about 2:1 to about 1:100 morepreferably from about 1:1 to about 1:75. The liquid nature of thegeminal alcohol aids in solubilizing the normally solid diol thus givinga product which is easy to compound into the corresponding polyglycidylether.

The polyglycidyl ethers of the present invention may be preparedaccording to the general technology disclosed in U.S. Pat. No. 4,110,354issued Aug. 29, 1978 to Bertram et al which is herein incorporated byreference. More specifically, the polyglycidyl ethers of the presentinvention are prepared by reacting equivalent amounts of epichlorohydrinto the starting alcohol. It is preferred that the epichlorohydrin beadded slowly to the starting alcohol in the presence of an acid such asboron trifluoride, tin tetrachloride, hydrofluoric acid or sulfuric acidto fully achieve the desired reaction product. It is, however, possibleto form higher polyglycidyl ethers due to the fact that some of theepichlorohydrin will add to the starting alcohol in a fashion such thatanother primary alcohol is produced which then may react with a secondmole of epichlorohydrin prior to the closing of the oxirane structurethrough the use of the base. Thus, chlorinated byproducts are therebyobtained. In the oxirane formation itself water and sodium chloride areliberated when sodium hydroxide is utilized as the source of strongbase. It is possible, however, to use other strong bases such aspotassium hydroxide or calcium hydroxide depending upon the reactionconditions and the tolerance for impurities in the reaction mixture. Theamount of the strong base employed is simply an equivalent amount asrequired in the reaction. The product may also be formed throughaddition of the corresponding allyl ether followed by oxidation to theoxirane.

The reaction to form the polyglycidyl ether is conveniently conducted indichloroethane although solvents such as toluene may also be employed.Following the closing of the epichlorohydrin structure to give theoxirane or polyglycidyl ether, the water so formed may be azeotropicallydistilled from the reaction mixture.

For the purposes of forming a fully cross-linked coating it is desirablethat the polyglycidyl ether contain 1.5 oxirane units or greater perstarting molecule of the alcohol. The figure, of course, is only anaverage of that required and a normal distribution will be founddepending upon the particular reaction conditions employed. Mostpreferably the product should contain two or greater oxirane units permole of the starting diol alcohol, most preferably 3 for the higherpolyols.

The addition of the epichlorohydrin should be conducted at as low atemperature as is reasonably possible to minimize the amount ofpolyglycidyl ether polymers formed. Desirably this temperature is keptbetween about 10 degrees C. and 50 degrees C., preferably from about 20degrees C. to about 25 degrees C. However, the reaction mixture uponfull addition of the epichlorohydrin in a dropwise fashion is preferablymaintained at from about 40 degrees C. to about 100 degrees C., mostpreferably from about 60 degrees C. to about 80 degrees C. during aperiod of from about 10 minutes to two hours preferably about 1 hour toensure a complete reaction of the components.

The products of the present invention are useful as curing agents foramines, amides, anhydrides, acids, mercaptans and the like. Suggesteduses of epoxy coatings are found in the publication of Federation Serieson Coatings Technology, Unit 20, Epoxy Resins in Coatings, published bythe Federation of Societies For Paint Technology, by Roy Al Allen,Copyrighted 1972.

The polyglycidyl ethers of the present invention have been found to beextremely light stable due to the absence of any aromatic structure ormethylidyne hydrogens in the geminal polyglycidyl ethers. The nongeminal polyglycidyl ethers of the present invention still enjoy thestability of the absence of aromatic rings.

The products of the present invention give epoxy cured coatings whichare found to have high gloss, great light stability and the absence ofchalking upon atmospheric weathering. The polyglycidyl ethers areobserved to have extremely low viscosity and therefore are highlysuitable as reactive diluents for other higher molecular weight epoxieswhich must otherwise be thinned with solvents. It is possible throughthe technology of the present application to form a 100% solids coatingwith the geminal polyglycidyl ethers of the present invention.

The following are examples of the present invention:

EXAMPLE I

The manufacture of the formyloctadecanol precursor is accomplished bycharging a 1 liter Magne Drive, 316 SS autoclave with 606 grams (2.26moles) of oleyl alcohol, 3.01 grams of 5% rhodium on alumina and 3 grams(9.68 moles) of triphenylphosphite.

The autoclave is sealed and pressurized to 10 atmospheres with nitrogenunder stirring and then vented to atmospheric pressure. The nitrogenpurge is repeated twice more to ensure removal of any oxygen present inthe autoclave.

The autoclave is then pressurized a third time with premixed carbonmonoxide and hydrogen gas in a 1 to 1 molar ratio to 68 atmospheres atwhich point heating is started. Stirring is manually controlled at 1250rpm and the uptake of the mixture of the gases starts at about 100degrees C. The reaction conditions are then maintained at a temperatureof 130 degrees C. and the gas pressure at 70 to 75 atmospheres.

The reaction is substantially complete after 4.6 hours and is determinedby the cessation of the gas uptake. The confirmation of completeness ofthe reaction is obtained by sampling the mixture and determining throughgas chromatograph analysis that there is less than 1% of the startingalcohol in the mixture.

The reaction mixture is then cooled to 75 degrees C., vented toatmospheric pressure and purged twice with nitrogen. The contents of theautoclave are then discharged at 75 degrees C. under nitrogen pressurethrough a pressure filter. The yield of the formyloctadecanol is greaterthan 90%. Atomic absorption analysis of the filtered product showed 244ppm of rhodium.

The reaction may be modified by using triphenylphosphine in place of thetriphenylphosphite. Alternatively, the oleyl alcohol may be substitutedfor by linoleyl or linolenyl alcohol. The reaction temperature may alsobe lowered to 90 degrees C. at which point the reaction takes asubstantially longer period of time to proceed. As a second alternative,the reaction temperature can be raised to about 170 degrees C. and thereaction time considerably lowered. However, some decomposition of theend product may occur above the 170 degree figure so it should not beexceeded.

In similar fashion the mixture of carbon monoxide and hydrogen may bevaried as previously described in the Detailed Description of theInvention and may also be varied between about 20 and 500 atmospheres ofpressure. The lower end of the pressure range of course, slows thereaction rate down while the higher pressure condition increases thereaction but also increases the probability that some of the startingalcohol will be saturated by the hydrogen.

EXAMPLE II

5.26 moles (1570 grams) of the formyloctadecanol obtained from Example Iis charged into a 5 liter glass round bottom reaction flask equippedwith a heat exchanger coil, thermocouple, stirrer, addition inlet,reflux condensor and combination glass electrode. A further reactioncharge of 695 grams (12.87 moles) of a 55.6% formaldehyde in methanolsolution is added under a nitrogen blanket. A 40% solution of sodiumhydroxide is made by dissolving 245.7 grams (5.95 moles) of sodiumhydroxide in 368 grams of water under a nitrogen blanket. The causticsolution is added to a charge tank and connected to the feed side of ametering pump.

The reaction mixture is heated to 30 degrees C. and the causticcarefully added by means of a metering pump with stirring to adjust thepH to about 10.9. After about forty minutes at 30 degrees C. theaddition of the 40% caustic solution is started at a rate of 9.65milliliters per minute and the temperature of the reaction is increasedto 60 degrees C. The addition of caustic required about 45 minutes andthe reaction temperature was maintained at 60 degrees C. Gaschromatograph analysis of a sample taken at this time indicated that thereaction was complete and that the gem-bis(hydroxymethyl) alcoholcorresponding to the formyloctadecanol is formed.

The reaction is held for an additional 20 minutes at 60 degrees C. aftercompletion of the caustic addition. The stirring is then stopped and thelower aqueous phase (816 grams) was allowed to separate.

After washing of the crude gem-bis(hydroxymethyl)octadecanol and itsdrying under vacuum the amount recovered is 1711 grams corresponding toa yield of greater than 90%.

Alternatively linoleyl or linolenyl alcohol derivatives of Example I maybe employed under similar conditions. The reaction temperature for theproduction of the bishydroxymethyloctadecanol is to use 6.43 moles ofthe 55.6% formaldehyde solution thereby yielding the correspondinghydroxymethyl formyloctadecanol as an isolatable product. This materialis then reduced through catalytic hydrogenation with copper chromite orthrough the use of lithium aluminum hydride to give thegem-bis(hydroxymethyl)octadecanol.

An alternative method of obtaining the bishydroxymethyloctadecanol is touse 6.43 moles of the 55.6% formaldehyde solution thereby yielding thecorresponding hydroxymethyl formyloctadecanol as an isolatable product.This material is then reduced through catalytic hydrogenation withcopper chromite or through the use of lithium aluminum hydride to givethe gem-bis(hydroxymethyl)octadecanol.

EXAMPLE III

The formyl alcohol of Example I is divided into separate streams and onepart is converted to the gem-bis(hydroxymethyl) alcohol of Example II.The second stream is hydrogenated by charging 1928 grams (6.46 moles) ofthe formyloctadecanol and a slurry of 108 grams of water-wet Raneynickel which has been washed twice with two 100 ml portions of ethanol.

The autoclave (316 SS) is sealed and pressurized to 10 atmospheres ofnitrogen with stirring. The autoclave is then vented and then purgedtwice more with nitrogen to ensure that the oxygen is substantiallyremoved.

The autoclave is then pressurized to 55 atmospheres with hydrogen andstirring is commenced. The temperature is controlled between about 100degrees C. and 116 degrees C. with the hydrogen uptake complete to givethe 9(10)-hydroxymethyloctadecanol (diol) in about 2 hours at a yield ofgreater than 90%.

The diol is then mixed with the gem-bis(hydroxymethyl) alcohol in thedesired proportions to give a liquid product.

EXAMPLE IV

The polyglycidyl ether of bis-hydroxymethyl-octadecanol is formed asfollows:

    ______________________________________                                        INGREDIENTS       EQUIVALENTS  WEIGHT                                         ______________________________________                                        Bis-(hydroxymethyl)octadecanol                                                                  1.00         114.7                                          Epichlorohydrin   1.00          92.5                                          Toluene           --           150.0                                          BF.sub.3.etherate  .03          4.3                                           NaOH (40% in water)                                                                             1.00         100.0                                          ______________________________________                                    

Half of the volume of the toluene, the bis-hydroxymethyloctadecanol andthe BF₃.etherate (borontrifluoride catalyst) are combined in a 1 literround bottomed flask fitted with a stirrer, condenser, thermometer andice bath. The epichlorohydrin is added dropwise over a period of onehour while the initial temperature is at 22 degrees C. and the exothermis controlled with the ice bath. The reaction temperature is maintainedat less than 25 degrees C. until all of the epichlorohydrin has beenadded and for an additional one hour.

The reaction mixture following the addition of the epichlorohydrin isthen heated to 70 degrees C. and held at that temperature for anotherhour.

The remaining toluene is then added to the reaction mixture and themixture is heated to reflux temperature. A Dean Stark trap is added tothe condensor and the sodium hydroxide is added over a period ofone-half hour. During and after the addition, water is azeotropicallydistilled from the reaction mixture. A total of 77 milliliters of water(99% of the theoretical present) is collected.

Following this distillation, the reaction mixture is then cooled toabout 30 degrees C. A large amount of sodium chloride and a waxyprecipitate were observed to have been collected on the bottom of theflask. The solution is decanted and filtered through cheese cloth. Waterand hydrochloric acid (0.1%) are added to neutralize the residual sodiumhydroxide present in the mixture. More waxy precipitate is then seen atthe interface and is removed.

The resultant polyglycidyl ether of the starting alcohol is then takento 100% solids under vacuum.

Following the above example, the following additional parameters shownin Table I the various results shown are obtained.

                                      TABLE I                                     __________________________________________________________________________    Bis-(hydroxymethyl)octadecanol                                                __________________________________________________________________________                            EPI           NaOH                                                     TEMP.  ADDITION                                                                             TEMP   ADDITION                                            RATIO                                                                              OF EPI TIME   NaOH   TIME   % TOTAL                          RUN SOLVENT EPI/OH                                                                             ADDITION                                                                             (MIN.) ADDITION                                                                             (MIN.) CHLORINE                         __________________________________________________________________________    A   Dichloroethane                                                                        1/1  60     120     85    100                                     B   Toluene 1/1  50     25     110    15     2.32                             C   Toluene 1/1  20     50     110    25     2.60                             D   Toluene 1/1.1                                                                              20     45     112     0     3.91                             __________________________________________________________________________                                    Ox                                                                SOLUTION    O.sub.2     EPOXY                                                 VISCOSITY                                                                            %    ON   GARDNER                                                                              PER                                       RUN SOLVENT (P. 25° C.)                                                                   SOLIDS                                                                             SOLIDS                                                                             COLOR  MOLECULE                          __________________________________________________________________________            A   Dichloroethane                                                                         1.7   96.7 6.9  1-2    2.0                                       B   Toluene 24.0   98.9 5.6  1-2    1.6                                       C   Toluene 32.0   100.0                                                                              5.6  2      1.6                                       D   Toluene  3.2   99.8 6.8  1-2    2.0                               __________________________________________________________________________     NOTES:                                                                        EPI indicates that the material added is epichlorohydrin.                     EPI/OH ratio is the equivalent amount of each of the materials added.         % Total Chlorine is that found remaining in the product and no                hydrolizable chlorine is measured.                                            Viscosity is shown in the column indicated by n.                              % Solids is that amount obtained following vacuum applied to the recovere     material.                                                                     The term Ox O.sub.2 indicates oxirane oxygen on solids.                       The Gardner Color is the standard test applied to mixtures and indicates      that this material is nearly water white.                                     The Epoxy Per Molecule indicates the oxirane content per mole of alcohol.

                                      TABLE II                                    __________________________________________________________________________    Hydroxymethyl octadecanol                                                     __________________________________________________________________________                            EPI           NaOH                                                     TEMP.  ADDITION                                                                             TEMP   ADDITION                                            RATIO                                                                              OF EPI TIME   NaOH   TIME   % TOTAL                          RUN SOLVENT EPI/OH                                                                             ADDITION                                                                             (MIN.) ADDITION                                                                             (MIN.) CHLORINE                         __________________________________________________________________________    E   Dichloroethane                                                                        1.1  55     330    70     240    --                               __________________________________________________________________________                                    Ox                                                                SOLUTION    O.sub.2     EPOXY                                                 VISCOSITY                                                                            %    ON   GARDNER                                                                              PER                                       RUN SOLVENT (P. 25° C.)                                                                   SOLIDS                                                                             SOLIDS                                                                             COLOR  MOLECULE                          __________________________________________________________________________            E   Dichloroethane                                                                        --     99.88                                                                              5.3  --     1.5                               __________________________________________________________________________     NOTES:                                                                        EPI indicates that the material added is epichlorohydrin.                     EPI/OH ratio is the equivalent amount of each of the materials added.         % Total Chlorine is that found remaining in the product and no                hydrolizable chlorine is measured.                                            Viscosity is shown in the column indicated by n.                              % Solids is that amount obtained following vacuum applied to the recovere     material.                                                                     The term Ox O.sub.2 indicates oxirane oxygen on solids.                       The Gardner Color is the standard test applied to mixtures and indicates      that this material is nearly water white.                                     The Epoxy Per Molecule indicates the oxirane content per mole of alcohol.

EXAMPLE V

The polyglycidyl ether of the diol is formed as in Example IV utilizingequivalent weights of the various reactants. This material is found tobe a low viscosity polyglycidyl ether containing more than 1.5 oxiraneunits per molecule on the average.

The alcohol employed in forming the polyglycidyl ether is that derivedas the diol in Example III.

EXAMPLE VI

The polyglycidyl ether of Example IV and the polyglycidyl ether ofExample V are separately cured utilizing diethylenetriamine.

An additional variation of this example is the curing of bisphenol Aepoxide through use of mixtures containing from 10 to 90% by weight ofthe respective polyglycidyl ethers described above.

The above example may be further varied through curing the polyglycidylether with phthalic anhydride, phthalic acid, a polyaminoamide, amelamine or mercaptan.

What is claimed is:
 1. The polyglycidyl ether of a polyol containing onaverage more than 1.5 oxirane units per molecule selected from the groupconsisting of:

    CH.sub.3 (CH.sub.2).sub.m [C(CH.sub.2 OH).sub.2 ].sub.n (CH.sub.2).sub.p [C(CH.sub.2 OH).sub.2 ].sub.q (CH.sub.2).sub.r [C(CH.sub.2 OH).sub.2 ].sub.s (CH.sub.2).sub.t CH.sub.2 OH

and mixtures thereof: wherein n plus q plus s are integers the sum ofwhich is from 1 to 3; t is 3 or greater; n, q and s are 0 or 1; and mthrough t are integers the sum of which is from 12 to
 20. 2. Thecomposition of claim 1 containing as an additional ingredient thepolyglycidyl ether of a polyol containing on average more than 1.5oxirane units per molecule selected from the group consisting of:

    H(CH.sub.2).sub.n CH(CH.sub.2 OH)(CH.sub.2).sub.k CH.sub.2 OH

where k is 3 or greater; and h plus k are non-zero integers the sum ofwhich is from 12 to
 20. 3. The polyglycidyl ether of claim 2 wherein thesum of h plus k is from 14 to
 18. 4. The polyglycidyl ether of claim 2wherein m, h, k and t each are 4 or greater.
 5. The polyglycidyl etherof claim 1 wherein the starting alcohol is9(10)bis(hydroxymethyl)octadecanol.
 6. The polyglycidyl ether of claim 2wherein the starting alcohol is 9(10)-hydroxymethyloctadecanol.
 7. Thepolyglycidyl ether of claim 1 wherein the polyol has the sum of mthrough t equal to 14 to
 18. 8. The polyglycidyl ether of claim 1wherein n and q each equal 1 and s is zero.
 9. The polyglycidyl ether ofclaim 1 wherein n and s equal 0 and q is
 1. 10. The polyglycidyl etherof claim 2 wherein H(CH₂)_(h) CH(CH₂ OH)(CH₂)_(k) CH₂ OH and CH₃(CH₂)_(m) [C(CH₂ OH)₂ ]_(n) (CH₂)_(p) [C(CH₂ OH)₂ ]_(q) (CH₂)_(r) [C(CH₂OH)₂ ]_(s) (CH₂)_(t) CH₂ OH are present in a weight ratio of from about2:1 to about 1:100.